Monoazo dyestuffs



U i ed States Patetftf MONOAZO DYESTUFFS Ernst Merian, Allschwil, near Basel, Switzerland,

signor, by me'sne assignments, to Saul & C0,, Newark,

1., as nominee ofFidelity Union Trust Company, executive trustee under Sandoz Trust No Drawing. Application December 21, 1953 7' Serial N0. 399,610 I Q Claims priority, application Switzerland December'24, 1952 r v 6 Claims. (cl; 250-207.5

g A 15 As azo components for the preparation of the'monoazo The present invention relates to'new monoazo dyestuffs ,dyesmfis according to the p 'e inYelliion use y be which dye acetate silk fibers, synthetic polyamide fibers made of the i Y S Ie Y amlfles f the e e d l h fib i pure b i le bl d mddish series which are free of groups conferring water-solubihty, brown shades, the dyeings of which are distinguished by for p the amines'whwh correspond to the formula excellent discharge properties and very good'fastness to 20 11 light, washing,- perspiration and sublimation. Amongst f Y 7 the new monazo dyestuffs thosewhich dye acetate silk H- N fibers in violet and blue shades, find a particular interest \CHFZ as, until now, neither violet nor blue dyestuffs of the y dispersion type are known, the dyeings of which are well 25 dischargeable and; have simultaneously a good. fastness to light. The new monoazo dyestuffs of the present invention correspond to the formula l v OH2 -Z ...R1N=NR2N I i g omi-z -t wherein R stands for a ben'Zeneradical which bears in position 2 a sulfonic acid fluoride group, in position ,4 a nitro group and imposition 6 a hydrogen or a'ha IogenF atom or a lower alkyl, a-tr'ifluoromethyl or a lower alkoxy group, R stands fora benzene radical, z stands for a hydrogen atom or a lower alkyl, a lower hydroxyalkyl, a lower alkoxyalkyl, a cyano, a lower cyanoalltyhalower difl-uoroalkyl, a lower polyfluor'oalkyl, a lower alkoyl, a lower alkoylalkyl, a lower alkylsulfonyl, a lower alkyl sulfonylalkyl, a lower carbamidealkyl, a lower carboalk- I oxyalkyl or a lower alkoyloxyalkyl group, and wherein the group CH:z is present in position para to N=N.

A preferred series of the new monoazo dyestuffsv the formula SOsF V CHs-Z OsN wherein y stands for a hydrogen or a halogen atom ore a lower alkyl, a lower alkoxy, an acetylamino or a tri- 0 fluoroacetylamino group, and wherein 2 stands for a hydrogen atom or a methyl, an ethyl, a propyl, a hydroxymethyl, a hydroxyethyl, a hydroxypropyl,avhydroxybutyl, a dihdroxyethyl, a methoxymethyl, a meth-oxyhydroxyethyl, a dim'ethoxyethyl, a cyano, a cyanomethyl, a di- 5 substituents non-conferring Water-solubility, with 1 mol of a tertiary amine of the benzene series which too may 6 carry further substituents non-conferring water-solubility.

Of special importance in carrying out the present invention are the diazo derivatives of the 1-amino-49nitrobenzene-2-sulfonic acid-fluorides which bear in position 6 a hydrogen, a fluorine, a chlorine or a bromine atom or a 10 methyl, an ethyl, a tn'fluoromethyl, a methoxyor an ethoxy group. These intermediates are new. Their production is described in my copending application, Serial No. 399,609, filed on even date herewith, now U. S.

Patent No. 2,794,833.

wherein y and 2 have the previously recited significances.

The coupling reaction of the diazo compounds with'the azo components is carried out in the usual way,preferably in anacid medium. The dyestuffs thusprepared 0 are filtered, washed and dried.

In order to obtain useful dyeing, compositions, the .r;-:;.obtained monoazo dyestuffs are preferably ground, if desired in the presence of inorganic and/or organic fillers, together with suitable dispersing agents. Valuable dyeing compositions can also be preparedlby mixing the dyestufi pastes in the moist state with suitable dispersing agents .and subsequently drying the mixture, for example, in an atomizing drier. a l

The following examples illustrate the invention with- 0 out, however, being restrictive thereof. In the. examples,

the parts and percentages are by weight, and the tem- :peratures are in degrees centigrade.

Example 1 7.'6 parts of sodium nitrite: are added in the'course' of 1 hour to 90 parts of concentrated sulfuric acid at -,60. The solutionis cooled to 10-20 and then diluted with 100 parts of'concentrated acetic. acid, whereupon 22 parts of l-amino-4-nitrobenzene-2-sulfonic acid fluoride are added at 10,- Then 100 parts-of concentrated 0 acetic acid are added dropwise, and the excess of nitrite .gis destroyed by means of 5 parts of urea." The diazo solution thus obtained is poured onto 250 parts of ice, and coupling is carried out with a mixture of 19 parts of N- hydroxyethyl-N-cyanoethyl-aminobenzene, 20- parts of ,55

hydrochloric acid and 20 parts of ice, The formed :anonoazo dyestufi is filtered off, washed free of acid and dried. A dark red powder is obtained, which, when recrystallized from ethanol, forms bluish-red rectangular leaveswith" a melting point of 177.

Hydrogen calcd. 3.83%; found 4.05%.

The new monoazo dyestufi corresponds to the formula BOrF V 'CHr-CHa-OH H I oHa-oHi-orc It dissolves in ethanol with a bluish red coloration Analyses .-Carbon calcd. 48.45%; found 48.40%.

have also excellent fastness 'to washing, to perspiration, to gas fumes and to sublimation.

Example 2 44 parts of 1-amino-4-nitrobenzene-Z-sulfonie acid fluoride are introduced into 350 parts of concentrated sulfuric acid. The solution thus obtained'is heated up, to 60 and 14 parts of sodium nitrite are added. When the diazotation is finished, the mass is poured onto 500' parts of water and 1000 parts/of ice, whilethetempera ture is kept below Coupling is carried out with a solution of 33 parts of N-hydroxyethyl-n-ethyl-aminobenzene in 100 parts of water, parts of 30% hydrochloric acid and '100 "parts of ice. The formed dyestuff is" filtered ofli, washed free of acid and dried. The new monazo dyestufi, when recrystallizedifro'm ethanol, forms violet rectangular leaves melting at 162-164". It corresponds to theformula dissolves in ethanol with a violet coloration and dyes acetate silk in violet and synthetic polyamide fibers in bluish red shades.

Example 3- 44 parts of 1-amino 4 nitrobenzene-2-sulfonic "acid fluoride are diazotized as: described in the preceding example and coupled in an anologous manner with 41 parts of l-(N hydroxyethyl -N -cyanoethyl)' --amino'-3- methylbenzene. The resulting dycstuif melts, recrystal lized from ethanol, at' 178-180 and corresponds 'to the shades fast to light, washing,'perspiration, gas fumes and sublimation.

' "Example '4 44 parts of l-aminor4-nitrobenzene-2-sulfonic acid fluoride are diazotized as described in Example 2 and coupled in an analogous -manner with.36i parts-of l-(N- hydroxyethyl-N-ethyl)-aminoe3-methylbcnzene. The re- Example 5;

i *iieaotmwg *4 Example 6 The procedure outlined in Example 2 is followed, except that the azo component is replaced by 27 parts of 1-(N,N-dimethyl)-amino-3-rnethylbenzene. The thus obtained dyestuft which corresponds to the formula melts, when recrystallized fromethanol, at.2222-25 and 'dyes acetate silk in violetshades;

' diethyl amino-B-methylbenzene.

Example 7 The procedure outlined in Example 2 is followed except that the azo component is.replaced by,33 parts of l-(N,N-

The thus obtained dyestuifwhichcorresponds to the formula SIOzF 'CHa CHI-CH;

melts, when recrystallized fromethanohat192-194" and I dyes' acetate silk in violet shades;

Example 8 The procedure outlined in Example 2'is followed, except that the azo component is replaced by 39 parts of l-(N ethy-l-N-cyanoethyl)-amino-3-methylbenzene. The

. thus obtained dyestuff which corresponds to the formula Theprocedure outlined inExample 2 is followed, -except that the azo-component is replaced by-45 parts of 1-(N,N-dihydroxyethyl)-arnino-2 rnethoxy 5 methylbenzene. The thus obtainedfdyestu'fi;which corresponds" to the formula melts, when recrystallized from-ethanol, at"1t58 "and dyes acetatesilk in welldischargeableviolet shades fa t to light, washing, perspiration'and sublimation. l 1

l 1 CHt-C H: IN

CHrCHr-CN' 1 melts, when recrystallized fromethanol, at=227 229 and It dyes acetate silk in well dischargeable,'reddish violet dyes acetatesilk inreddish violetshades.

' Example 9 "The procedure outlined in Example 2 is followed, ex-

cept that the azo component, is replaced by 39 parts of 1' -(N- methoxyethyl N ethyl) amino 3 methylbenzene. The thus obtained dyestuff, which corresponds to theiformula SOzF CH:

CHz-CHr-O-CH:

CHI-CH! melts, when recrystallized'from ethanol-,iat 168 170 and dyes acetate silk in violet shades.

Example 10 The procedure outlined. in Exampleiisfollowed, except that the azocomponent is replaced by 42 parts of 1 (N 2,3' dihydroxypropyl N ethyl) amino 3- methylbenzene. The thus obtained dyestuff which corresponds to the formula CHr-CH:

melts, when recrystallized from ethanol, at 189-190" and dyes acetate silk. in violet shades.

Example 11 Theprocedure outlinedin Example 2 is followed ex,- cept-that; the azo-component is replaced by-48,vparts of l (N hydroxyethyl N butyl) a amino 2 methoxy- S-methylbenzene. The thus obtained dyestutf which corresponds to the formula V I SOIF CHI OCH:

CHr-CHr-OH OaN- CHr-CHs-OHr-OHa melts, when recrystallized from ethanol, at 62-66? and dyes acetate silk in reddish blue shades.

I Example 12 The procedure outlined in Example 2 is followed, ex-. cept that the azo component is replaced by 48 parts of 1 (N,N dihydroxyethyl) amino 3 acetylaminobenzene. The thus obtained dyestuff which corresponds to the formula NBC CHa QHs- CHz-OH OzN N CHr-OHrOH melts, when recrystallized from ethanol, at 190 and dyes acetate silk in violet shades which are fast to light, washing, perspiration, gas fumes and sublimation and are well dischargeable. I

Example 13 The procedure outlined in Example 2 is followed, except that the azo component is replaced by 54 parts of l (N,N dihydroxyethyl) amino 2 methoxy acetylaminobenzene. The thus obtained dyestufi' which corresponds to the formula soir rmoocm om-cm-on 02N- N=N N\ cm-om-on CH] melts, when recrystallized from ethanol, at 204 and dyes acetate silk in greenish blue shades.

Example 14 SlO F is soluble with a red coloration in ethanol and dyes acetate'silk in red shades. --It melts, when recrystallized from ethanol, at l6 3-l65 CHPCHr-OH CHe-CHF:

6 Example 15 e The procedure outlined in Example 2 is followed, ex

cept that the azo component is replaced by 41 parts of 1 (N hydroxyethyl N 2',2' difluoroethyl) amino- 3-methyl-benzene (dissolved in 80 parts of 30% hydrochloric acid without addition of water and ice). The

thus obtained dyestufi which corresponds to the formula SO31 CHI OIN , CHg-CHF,

is soluble with a ruby coloration in ethanol and dyes acetate silk in ruby shades. It melts at 199 and forms longish redbrown lances when recrystallized from ethanol.

Example 16 a om-O-rhn-Orf is soluble with a ruby coloration in ethanol and dyes acetate silk in reddish violet shades. It melts at 218-219 and forms long, very thin carmine needles when recrystallized from ethanol.

CHz-CHr-OH CHr-CHFOH Example 17 The procedure outlined in Example 2 is followed, ex-

cept that the azo component is replaced by 39 parts of p 1 (N,N dihydroxyethyl) amino 3 methylbenzene. The thus obtained dyestuif which corresponds to the formula SOrF CH:

OzN I CHr-CHa-OH cni-cm-on I is soluble with a violet coloration in ethanol and dyes acetate silk in violet shades. It melts at 204-206 and forms violetbrown needles, when recrystallized from ethanol.

Example 18 j 17.5 parts of l-amino-6-chloro-4-nitrobenzene-2-sulfonic acid fluoride are introduced at 60 into 180 parts of 9.5% sulfuric acid and, under stirring, diazotized by addition of 5 parts of dry sodium nitrite. Some time afterwards the solution is cooled down tov 20 and poured onto 750 parts of ice and 250 parts of water. The excess of nitrous acid is destroyed by addition of aminosulfonic acid and then coupling is carried out with a solution of 16.5 parts of 1-(N,N- dihydroxyethyl)-amino-2-methoxy- 5 -methy1benzene in 10 parts of 30% hydrochloric acid and parts of water. The new monoazo dyestuff which precipitates, is filtered, is washed free of acid and is dried. It dissolves in ethanolwitha violet coloration and melts, recrystallized from'ethanol, at 162-165. The

dyestuflf corresponds to the formula son? 0H:

(Bl I \CHFCIHT-OHIII fast to light, to washing and to sublimation.

Examples 1 9-106 Infthefollowing table further monoazo dyestuffs are andflyesacetate silk in well dischargeable; violet shades recited whichmay be produced in an analogousmanner as described in the foregoing examples. They corre spond to the formula sol Y1 wherein-X, Y Y Z and 2,, have the significances de- The term color represents the coloration of the dyestufi solution in ethanol.

10' fined in the table.

Example 107 10 parts of the dyestufi according to Example 12 are well ground together with 10 parts of a dispersing agent and 5 parts of sodium sulfate, whereupon this mixture is added to a dyeing bath containing 10,000 parts of water at 45. When the dyestufi is well dispersed, 30,000 parts of water are added to the bath and dyeing of 1000 parts of acetate silk is started at 50. The temperature is elevated preferably up to 80 and dyeing is continued for about 1 hour. The material is then soaped, washed, rinsed and dried. The shade thus obtained is a pure violet possessing very good fastness to light, washing, perspiration, gas fumes and sublimation. The dyeings are well dischargeable.

Example 108 Example 109 In an analogous manner to that described in Example 107, 1000 parts of nylon polyamide fibers are dyed. The temperature is preferably elevated up to the boil. The shade thus obtained is a pure ruby of good fastness to washing and sublimation.

Having thus disclosed the invention, what is claimed is:

1. A monoazo dyestufi which corresponds to the formula OaN N= N CHr-Z CHa-CHa-OH wherein y stands for a member selected from the group consisting of hydrogen, chlorine, bromine and lower alkyl and wherein z stands for a member selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl,

3. The monoazo dyestufi which corresponds to the formula SOxF CHx-CHr-OH 4. The monoazo dyestufi which corresponds to the formula som I CHr-CHz-OH Cl 5. The monoazo dyestuff which corresponds to the formula CHPOHr-OH OIN SOgF

CHI-0 OsN CHPCHa- OH 6. The monoazo dyestuff which corresponds to the formula som GHr-CHr-OH OaN OKs-CH:- OH

References Cited in the file of this patent UNITED STATES PATENTS Schweitzer et al. Apr. 11, 1939 Parker et al. u Nov. 20, 1951 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,830,043 April 8, 1958 Ernst Merian It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 64:, for dihdroxyethyl read dil1ydroxyethyl; column 3, line 12, for N-hydroxyethyl-n-ethyl-aminoread N-hydroxyethyl-N-ethylaminolines 36 to 39, Example 3, the left-hand portion of the formula should appear as shown below instead of as in the patent SOQF Signed and sealed this 26th day of August 1958.

[SEAL] Attest: Y 7 v KARL H. AXLINE, V I ROBERT C. WATSON,

Attestz'ng Oyfioer. Oomz'ssz'oner of Patents. 

1. A MONOAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 